Preparation of varnish compositions



July 2, 1946. A. E. RHElNl-:ck E-rm.A 2,403,300

I PREPARATION OF VARNISH COMPOSITIONS Filed .my 2s, 1942 @u w www HTOP/VE/ Patented July 2, 1,946

v.U' 1\n'1r.o "STATES PATENT OFFICE PREPARATION F vAnNIsH COMPOSITIONS Alfred Rheineck and Samuel B. Crecelius, Louisville, Ky., assignors to'DevoeA & Raynolds Y Company, Inc., a corporation of New York Application July 28, 1942, Serial No. 452,660

Claims.

AIn the manufacture of varnishes,` the classical method has been to heat together or runf a natural resin with an oil such as linseed or tung oil. Hydroxyl bearing oils, especially castor oil, have been suggested for use in making varnishes, but ythese-oils do not have proper drying qualities and before being used, must be subjected to a process of dehydration whichis ordinarily carried on by the aid of catalysts or other reactants.

We have discovered that very ne varnishes can be made simply by heating together an acidic resin, such as rosin, and a' hydroxylated oil, such as castor oil (or the oil. acids) kand 4carrying on the heating for asuiiicient length of time at a proper temperature. Subsequently the acidity is removed by esterication with a polyhydric alcohol such as glycerine. The resulting product;

lsurprisingly enough, has excellent drying qualities and in fact is better than most of the oleo* resinous varnishesf' Castor oil is the most readily available hydroxylated oil, `but the invention is applicable to other hydroxyl bearing oils or oil acids which may be synthetic bodies,`such for example as dihydroxy stearicr acid or its polyhydric alcohol esters, or hydroxylated natural oils.

Rosin is the most readily available acidic resin vHS top limit is the practical temperature at which the oil will darken materially, say about 350 C. A good working temperature is between 290 C. tlridV 325 C. and we preferl to operate at about The Atime of treatment will vary from about 31/2 to 8 hours, depending upon the relative proportions of oil andresin. The long oil varnis'hes require a longer time. The oil and'resin may be heated in simple mixture, preferably in a closed vessel provided with a stirrer. However, we nd that the use of a small amount of inert solvent is of assistance as Water is given 01T during the 4 treatment and the solvent helps to remove the Water. In practice the solvent is condensed, separated from the Water and returned to the vessel. When our process is carried out, if a study is madev of the acid values of a mixture' of rosin and a hydroxylated oil such as castor oil, interesting factors may be noted. As the temperature rises to about 270 C. the acid number rises quite rapidly, probably due to the evolutionV of volatile ingredients. This may occur, for example, duringabout the iirst half hour of heating. Thereafter for about 2 to 21/2, hours (aiJ va temperature of Yabout 280 Cuor higher, say about 300 C.) the acid number drops quite steadily but other natural resins may be employed either in their normal state or in modiiied form provided they are acidic in their nature. Thus fossilV resins may be used which have been heated or frun to increase their acidity and solubility in oil. vVarious modified forms of rosin or other natural resins which may be used include the maleic anhydride adducts and the nonesteriiied rosin modiiedy phenolic resins. In these cases the rosin still vretains its acidic nature, and there- .fore is available for our process., An example of an acidic resin of a synthetic nature is licanic acid resin. These examples are given as illustrating what we mean by the'term acidicresins. In addition to the acidic resins, other nonacidic resins can be included either from the beginning of the operation or maybe added subsequently, but theyapparently do not takepart in the reaction and therefore are only used in conjunction with acidic resins. The proportion ofresin to oil may vary over wide limits, but ordinarily should fall within the range to give a varnish of useable oil length. Thus the composition may vary from 5 to 50- gallon oil length proportions. f.

In order to accomplish our result, the hydroxylated oil and the acidic resin must be heated above a temperature of about 270 C. andthe and after reaching a minimum, it again rises appreciably and may even reach a figure approximately as high as the initial ac id value. We know that the `process is complete when the rate of riseof the acid number becomes v ery slight, Whichjindicates that any reaction that may be taking place has been substantially completed. While approximately complete reaction is desirable, as indicated by the acid number reaching substantial equilibrium, still results of some value may be had short ofthispoint. However, in any event theheating should 'be conducted at a temperature of'between'about 270 C. and 350 CJ and should be continued until the acid number of the mass has risen substantially above its minimum value. Y i

- For the purpose of illustration, we showin the accompanying drawing curves for four different f rosin-castor oil mixtures in which acid values are plotted against Vtime of treatment. In all cases the'oils ywere heated so that they reacheda temperatureV of about 270 C. in just under half' an hour and reached a temperature of-about 300 C. in not over 1 hour and that temperature.

In this drawing, the vcurve designated by the numeral I representsa` l121/2) gallon varnish. that iavafrnish made. up of 121/2 gallons of oil with then were held -atabout poly ethers such as until the acid Value become substantially con- Y stant. We find that it is not necessary' topar'ry the heating all the way to thispoint lbut...something approximating this point, say to a'poin'tas indicated by the line EF, will ordinarily.v be sufi-1 fcient. As indicated in the drawing, this took from about 4 to 61/2 hours but with 'Vr't'ryi'ri'gternr`r peratures and differentV proportions of-.ingredients this may take from`31/2 to 8 hours. t

Mier. this, phase ef the. `treatment has..been Carried tothe peint indieateijthe;aeidnumber ef the mixture .is ascertained. and @sieht-excess of polyhydricnalcohol isv added, .We here use the term polyhydriclalcohol as indicating an al'cohel having mere -thenwe evaileblehydrexyl groups.l Thus we may (21111110.57 glycerol, mannitol, .sorbitoL erythritol, pentaerythritol andits dipentaerythritol orpolypenftaerythritohinositol or` other `similar alcohols. The` esterieeten .with this; .elehel .is ,Carried out in known manner preferably `at La temperaure in the order-of about 300 C. andthe heating is continued `even after esterication is cornpleted until' the oil in the Varnish is sufficiently bodied. Forpexarfnple, VWe hatefoundthat excellent results are had if after KVthe finished varnish isthinned `to, 50% solids with mineral spirits, it hasa viscosity of about E on the Gardner-Boldt stirring for 6 Value Was 77.

tion of a 12-gal1on varnish made from castor oil and rosin.

FIRST STEP Parts Castor oil l 500 Rosin (WG) 4i?) Solvesso #2 referred to in this land certain of the following examples is an aromatic petroleumpaphtha having a boiling Sncoitm STEP The tenet @het estad timmizftots. n Thisvarnish and those which 4follow y'contained .5% Pb and .04% coa-suffers uni-ess `t'tiietvvise in(ligated.v

The fouowmg example :illustrates 'theiiprreparation of'a 22 ganen vamisn by lengthening the scale. As the oil length increases, carefmust be Y exercised during the last reaction toavoidv gelation before esterification is Yconlpleted.v ris usually accomplished by using the lower'esteri'- iication `temperature's and gradually raising 4the 'Vtemperatureas reaction becomes complete. Or-

dinarily additional heating to gain body is unnecessary. Various'aids to esteriiication may be employed suchl the gus'eo'f small amounts of inert solvents or blowing an inert gasV such as carbon dioxide through the mass, o-r etten esterication catalysts. n y i l l The foregoing description covers the'essential features of our invention butobviously various modiiications maybe employed.v Thus in place of castor oil, we may 'employ castoroil vacids which are subsequently esteried with polyhydric alcohol. Also instead of using a natural hydroxylatedoil such as castor oil, synthetic hydroxyl bearing oils may be employed, such` for example as dihydroxy stearic acid or ester of Vthis acid. I

It is also possible afterthel primary* treatment of the hydroxylated oil (or oil acids) hasbeen carried out, to add additional resinous ingredients or additionalV oils. Thuslthe oil lengthiof.the

Vtarnish may be reduced by'ad'ding natural 1resins or synthetic resin such as phenolic resins and the oil length may be lengthened byadding other oil s uch as linseed oil or the like.Y Hydroxylated product of the erst step in Example-1." 1

Pro-duct (first step 1 The mixturev ,was heated 'hours at'240" HC. 'pg-ille final Varnishfhad the following constants:

Viscosity` j -F This varnish dried to ia, goo-dfl-m in 1 -hours .which was better 'thanthe standard made by vother' methods.

ammette V y The following-example illustrates the prepara'- tion of fa i9 gallon varnish 'made Afrom aproduct approximately "as indicated in the iirst step of Example I. Y l v ebenen@ tasa tdtljff Glycerol The phenolic base-for this example Was lmadelby f heating the following -for 2 hours.

oils may also be prepared bytreating naturalojils withoxidizing agents.

Detailed methods of carrying out our can readily be understoodffrom the following illustnative examples: Y Y

` The following example illustrates the prepara'- yParts and agitation 8 hours starting 25'0'C. 'andglairl' mgfzfao" C; ma `houtsfand herding here'for'tne remaining Shours. j

The final v rnish hadnthe followinglconstants:

a wat 'fainting and' hours at 300 C. The iinal acidk which `was bettery thanwthe .standard madegby other methods. V n l Iv rIv'he following example illustrates the preparation of a 21 gallon varnish made from castor. oil and rosin.

FIRsT STEP i, u Parts Castor oil l 1,500 Rosin 800 Solvesso #2 40 The mixture was heated for 61/2 hours at 300 C.

The final acid value'was 55 when 75 parts of water were evolved.

SECOND STEPl f g Parts Productfrom first step 1,097 Marmitol 52 Mineral spirits v 20 The mixture was heated for 14 hours at 240. C. The final varnish had the-following constants:

Acid value 5.5 Viscosity F-G 'fIhe varnish dried to a good lni in 3 hours.

The following example illustrates the preparation of a lio-gallon varnish made by ,heating v castor oil with rosin.

FIRST STEP Parts Castor oil 1,500 Rosin v 447 Solves'so #2. l40

This vmixture was heated forj7 hours at 300 C. The final product had an acidvalue of 39,7 and 74 parts ofv water were evolved.

SECOND STEP This mixture was heated -`for3"hours`between 2-70C. and 300 C., gainng`300 Cfduring this period. The final varnishhad theefollowing constants: Acid value 4.8 yViscosity s' Q This varnish driedto e goed mm in 5 hours.

EXAMPLE/V1 The following example illustrates thepreparation bf a 5o-gallon Varnish made by heating- CfavStOl. 011 with 10sin l FIRST STEP Parts4 Castr'oil l 1,500 Rosin' 325 This mixture was heated fors hours et 300v C. es

The nal product had an acid value of 33', and 75 Darts of water were evolved.'v

SECOND STEP l -v 'l' 'f `-Pa1ts Productfrom rst step 450 -v Dipentaerythritol 12.7

`The mixture was esteriiied Vfor minutes at ith stirring, and passageor arbon. di-

was I thinned to partsxylene and mineral spirits. z

The lvarnish hadthe following constants:

5,0% solids with equal Viscosity-' Acid value 7.6

This dried tot geedim in 24 heure when treat. ofrPb and .03% Co as driers.

ed with .5

- Y EXAMPLE VIIv f The followingr example illustrates the lreparation of a. r22-gallon varnish made by heating castor oil and a `run congo resin.

.FTIRSTSQE? u Parts Castor4 oil 1, 500 Run congo resin..l 805 Solvesso #2 30 This Ihixturewas heated to 300 C. for'7 hours. The inal acid value of the mixture' Was'l25 and 72 parts of water were evolved.'

SECOND STEP r Parts Product froml :first step r k 8004 Pentaerythritol -T 17 Mineral spirits 40 lThis mixture was heated Vfdr 4 hours at 235 C. :sov

The final varnish ha Acid Va1ue' l Viscosity the following constants:

The following ration of a iO-gallon oil, fatty acids and rosin.

FIRST STEP i. .Parts ,Castor oil fatty acids ,1,435' Rosin 447 SOlVeSsO #2 30 This mixture was lheated for 5 hours at 300", C.

The nal acid value was 155.

SECOND STEP p Parts' Products'from rst step 800 Glycerol 71 Mineral spirits `40 The mixturev was heated 7,1/2"hours ,as 235 "C. 'I'he final varnish had the followingv constants: Acid value Y l Viscosity ...Lm-. y' i This varnish dried to a goodlrn inz5 hours.

The following exam-ple illustrates the preparation 'of a, 20-gallon varnish-from hydroxylated oleic acid (9-10 dihydroxy stearic acid) and rosin. p

The oleicacidand base werel reactedin 1.000

parts ,Qi water, andthe. permanganate was dis- .solved in 3,000 parts of water. The soap :salu-1` example illustrates the prepavarnish made from castor K of thepe'rmanganate was s 1 ture Vdid notrrise above 5 C. water was added as l came a purewhite.l

gaining 300Y at 260 t0 270 tion'was' cooledto below 5 C2 'and the pei-inanganate solution added. THe-'rate of addition "ueh that the tempera- The /ren'iainingn ice. This reduiredabout 3 Vhours under constant agitation. Sulphur dioxide was passed into the mass until the mass be- Thel slidswe'i'e coagulated by gentle heating,- freed-i of the excess liquid and washed severaltimes with hot water. l.The hard mass was .dispersed lin petroleum ether, and

gently heated anditered. This solid remaining v was the 9-10 dihydroxy'stearic acid.4

SECOND STEP f- 1 Parts Diiiydroxy'stearie aeid ieg Rosin 89 Partsl Predutfrm seeded step. 1781 Glycerol `This mixture washeated together for 3 hours C. Tliev final acid value was 10,

andviscosty was .A at '75%- solids. Thisdried to a-,dryvlmiri 24hours. j

e EXAMPL'X The following example illustrates the preparation of about a 25-gallon varnish from hydroxyll'l'rdtrl'e'iirl i FIRST STEP. Thew hydroxylated: trible-in. wasA prepared:

:This mixture was. gently heatedi for 2l hours when the solution; became homogeneous.` It was 'further heated wtiigeritie feiiuxingifor amore" hours." Upon oolirigftl'ie mass was' 'washed with several portions-f ofsalt water.- 'Ifheoily mass y was extractedi with-.several lportions of petr'oleunfi-y ether.- Thelheavyoilwas then reedof. any dise solved Vpetroleum ether-.-

vSncoND ST-EP- Y Y 'if Parts v Hydreyiat'edf teieiein..; 365' Rosin Solvesso #3 (boiling point 345 F.V to

410F.) 1 y `5 This mixture was reuxed for' 2A hours -alt-251) C. and then heated to 300 C. and held-for'-; 6- hours;- until the acid value remained constant atll. v Y f- Y Y The following exampleY illustrates the preparatin Of Varnish mad VO'I'I hyd-'Sf'lljd ya bear-i oil arid rosi-n.

' Parts.

Castor -I .Unesteried modiie'dN henolic resin 890 fSolvesso #12 70 Vfollows: v Y Parts Triolein 435 Acetic acid-glacial v 2 75 Hydrogen proxid'e-30'% 1`, 500

est

f in

me@ STEP, Following the method of Example X, first stepg the following were used to preparel hydromflsltte'dI y soya bean-v oil.:

This. mixture was heated to 300 C. in about' an hour and-'held atthis; temperature for hours.' `when the acid value Vremained constant at 56.-

This mixture was heated', together withstirring `and passage of inert gas.' for '7 hoursat 275 C. The nal acid value was 5'.- Thi's dried`A` to a good film in 24 hours..

EXAMPLE XII 1 The following example illustrates thepreparaef tion of a 20-ga11on varnishmade from castor oilr and an unesterified modified phenolic resin.

` FIRST STEPY 1 (-The'resm used in this exemple isknow'nas Arochem 385-. Itis rosin combined withabouti 15% 'of a phenolicbase.)V

refluxing for '7 hours att-300 C. .The final acidr value was 417.4 anclparts( ofwater were AcidU Vvalue Viscosity rThis driedito a good Aillm in 10 hours with 5% PbL and .03% Colas'driers.

This example illustratesvthe: preparation of a 22-gal1on varnish made from castoroil and a maleic anhydride rosin resin.

FIRST STEP-v oastor oi1 j 1,500AAV Maren. resi-n resine 'iii 46 Solvesso #2 The resin and yoilwere heated. together with- Parts (The resinused in thisexample was made by reacting 1500 parts of rosin with 170 parts of maleic anhydrideat .20' C. to 210 C. for 30. minutes.)

The vresin andv oil were refluxing for 7 hours at 300 heated together `with C. The final acid value was 55.4. The. theoretical water was evolved.

SECOND STEP Parts Product (iirst step.) 660 Glycerol (98%) 22 This was heated with stirring and passage of inert gas for 7 hours at 240 C. This was thinned to 50% solids with mineral spirits. The iinal varnish had the following constants:

Viscosity T Acid value 10.3

When treated with .5% of Pb and .03% Co as driers, this varnish dried to a good i'llm in 10 hours.

EXAMPLE XIV This example illustrates the preparation of a -gallon varnish made from castor oil and the resin of Example XIII.

FIRST STEP Y Parts Castor oil 300 Resin (Example XIII) 715 Solvesso #2 40 This mixture was heated to 300 C. for 31A hours nish solids were thinned to 50% solids with mineral spirits. 'I'he iinal varnish had the following constants:

Acid value 9.4 Viscosity D In this case we use the term oily oil-acid compound as specifically covering the acids of natural, .animal or vegetable oils, or their polyhydric alcohol esters, thereby including the oils themselves. The term oily is intended to describe the material when in the liquid phase. Thus the term oily hydroxylated oil-acid compound is intended to be generic to materials such as ricinoleic acid or dihydroxyY stearic acid or the like or their esters such as castor oil or other hydroxylated natural oils, and also to synthetic polyhydric alcohol esters of these acids. Certain of these bodies are solid at normal temperatures but when brought into the liquid phase they may properly be described as oily.

What we claim is:

1. A process for making useful varnish bodies Which comprises the steps of heating together castor oil and rosin at 290 C. and 325 that .the rosin will react with the castor oil and continuing the heating for more than 31/2 hours y 4and until the acid number of the mass has risen substantially above its minimum value and until the rate of rise of the acid number is very a temperature of between C. and under conditions such hydricalcohol,4 i l 2. A process as specified in claim ,1 in 'which the mass is esteriiied'with, glycerine. Y In theprocess of making useful varnish bod- .ies the step which consists in heating a substance selected from the group consisting of the hydroxylated natural oils and the hydroxylated fatty acids of such oils witha resin of acid reaction having free carboxyl groups adapted to combine with the hydroxyl groups of such iirst selected substance ata temperature of between 270 C. and 350 C. and under conditions under which 4the resin Will react with such iirst selected substance, and continuing the heating for more than 31/2 hours and until the acid number ofthe mass has risen substantially above its minimum value,

4. In the process of making useful varnish bodies the steps which consist in reacting a substance selected from the group consisting of the hydroxylated natural oils and the hydroxylated fatty acids o-f such oils with a resin of acid reaction having free carboxyl groups adapted to combine With the hydroxyl groups of such first selected substance at a temperature of between 270 C. and 350 C., continuing the heating for more than 31/2 hours and until the acid number of the mass has risen substantially above its minimum value and then esterifyingl with a polyhydric alcohol.

5. A process as speciiied in claim 4 in which the temperature of the first step reaches a point between 290 C. and 325 C. and the heating is continued until the acid number becomes approximately constant.

6. A process as speciiied in claim 4 in which the resin used is rosin.

7'. A process as specified in the resin used is resin hydride.

8. A process as specified in claim 4 in which the ilrst -substance selected is castor oil andthe resin is rosin reacted with maleic anhydride.

9. An intermediate varnish compound consisting of the reaction products of a substance selected from the group consisting of the hydro-Xylated natural oils and the hydroxylated fatty acids of such `oils reacted with a resin of acid reaction having free carboxylic groups adapted to combine with the hydroxyl groups o1 such first claim 4 in which reacted with maleic anselected substance and heated at a temperature between 270 C, and 350 C. for more than 31/2 hours and until an approximate equilibrium of acid value is reached, the ingredients being present in proportions equivalent to between 5 and 50 gallons of oil per pounds of resin.

10. A varnish body consisting of the esteriiied reaction products of a substance selected from the group consisting of the hydroxylated natural oils and the hydroxylated fatty acids of such oils, reacted at a temperature of between `270 C. and 350 C. with a resin of acid reaction having free carboxyl groups adapted to combine with the hydroxyl'groups of such iirst selected substance in proportions equivalent to between 5 and 50 gallons of oil per 100 pounds of resin and heated for more than 31/2 hours and until a pointvof substantial equilibrium of acid value is reached, and subsequently esterifed with a polyhydric alcohol, such body being characterized by its excellent drying qualitiesy and low acid number.

11. A body as speciiied in claim 10 consisting of the esteriiied reaction product of castor oil and a resin comprising rosin.

a minimum value and Vprflxinlfatell'y the same the .drigiixaf'l @91d valu@ and subsequently esrfyng th rulting mas 1.4, The nrQces describy d ,in Claim 1.2 inwhh the polyhydric alcohol is pentaerythtol.

1,5- The process described in claim 12 inzwhich the polyhydricalcohil a polypentarythritol.

' ALFRED E- vSAMUEL B. 

